Surface-active compositions



Unite 2,103,197 K SURFACE-ACTIVE COMPOSITIONS Herbert L. Sanders,Phillipsburg, N. 3., assignor to General Aniline & Film Cprporation,.NewYork, N. Y., a

corporation of Delaware No Drawing. Application December iii, 11949,

- Serial No. 133,223

9 Claims. (Cl. 260=-i) Thisinvention relates to novel surface-activecomposi-- CH CHr-NH;

CH-CH:

The compositions of this invention are the condensation products of theaforesaid amine with 4 to 40 molecular equivalents of ethylene oxide.Condensation of ethylene oxide with the aforesaid primary arrune resultsin replacement of at least one of the hynrogens of the amino group, andgenerally both or them, by a polyethenoxy chain radical. Thecompositions are conveniently obtained by introducing ethylene oxidenito dehydroabietinyl amine in the presence of a catalyst promoting 'theformation of polyethenoxy chains, particularly an alkaline material suchas an alkali metal alcoholate or hydroxide, advantageously at atemperature from 120- 180 C., until 4 to 40 mols of ethylene oxide areabsorbed.

. Similar products can be produced by condensing the aforesaid aminewith ethylene glycol, a polyethylene glycol or an ethylene halohydrin(e. g., ethylene chlorohydrm) instead of ethylene oxide. Condensation ofglycol or polyglycol with the amine can be effected by heating in thepresence of a dehydration catalyst such as bleaching earth, activecarbon black and the like, while ethylene halohydrins can be condensedwith the amine 1n the presence of alkaline materials serving ashydrogen-halide acceptors.

The condensation products thus obtained are v1scous liquids to waxysolids, soluble in water and showing surface-active properties therein.Compositions in wh ch the number of ethylene oxide radicals per mol ofamine is near the lower end of the range specified above are Ollsolubleas well as water-soluble.

Those compositions which contain 8 to 30 ethylene oxide radicals per molof amine have outstanding detergent properties, especially in washingcellulosic materials such as cotton. For general utility as detergents,those products having 8 to ethylene oxide radicals per mol of amine arepreferred. Compositions having 8 to 30 ethylene oxide radicals per molof amine are also soluble in aqueous hydrochloric acid (e. g. having aconcentrat on of 15%), and are effective as mhibnors 1n the pickling offerrous metals. For the latter purpose, products having 16 to 30 mole ofethylene oxide per mol of amine are generally preferred.

Condensation products having 33 to 40 mols of ethylene oxide per mol ofamine are valuable as emulsion .breakers for water-in-oil emulsions ofthe type encountered in petroleum refining.

The following examples, wherein parts are by weight,

2,703,7 1 Patented Mar. 8, R955 illustrate a preferred method for tionproducts of the invention.

EXAMPLE 1 59 partsof dehydroabietinyl amine (e. g. a commercialproductknown. as Rosin Amine D") in admixture with 0.18 part of sodiummethylate, were heated at 155- 165 C., and 101.7 parts of ethylene oxidewere passed into the mixture over a period of 5% hours at a gaugepressure of 5 to 10 cms. of mercury. A water-soluble product was thusobtained having an average of 8 to 9 ethyleneoxide radicals permolecule. The product was a viscous liquid of light tan color andpossessed only a slight odor.

The product of this example was subjected to a Launderometer test inwhich its washing power for cotton goods was compared undersimilar testconditions with the acetate of the intermediate dehydroabietinyl amine,and with a commercial alkylphenol polyglycol ether noted for exceptionaldetergent properties. The cotton cloth employed in the test was soiledso as to provide a reflectance of 52%. Concentrations of the variousdetergents ranged from 0.05 to 0.5%. After washing with the aforesaiddetergent, it was found that theN-polyethenoxylated dehydroabietinylamine of this example, as well as the preparing the condensaalkylatedphenol polyglycol ether, increased the reflectance of the cloth to 66 to69%, whereas the acetate of dehydroabietinyl amine increased thereflectance to only 53 EXAMPLE 2 A series of condensation products ofethylene oxide with dehydroabietinyl amine were prepared in a mannersimilar to that disclosed in Example 1. The mol ratio of ethylene oxideto dehydroabietinyl amine was varied from 4 to 37 in the series. Theproperties of theproducts are given in the following tables.

Table I Ethylene Products Oxide/Amine Form Clarity Mol Ratio 4 ViscousFluid Translucent. 18 Liquid and Solid D0. 28 Pasty S0lld. Opaque 32Waxy S0lid Do. 32 do D0. 37 do D0.

Table II Freezing pH (1'7 Products Range, Aqueou s 0. Solution) TableIII Foam test (0.05% of aqueous solution) [Height of foam in mms.]

- After Alter After Products Imtm] 30 Secs. 2 Mine. 3 Mine.

The products were tan to cream colored and had only a slight odor.

As indicated in the foregoing examples, the condensation products of theinvention are suitable as washing or foaming agents, and in addition,are suitable for emulsi- .fying and wetting purposes radicals per mol ofdehydroabietinyl amine.

3. A composition as defined in claim 2, having outstanding detergentproperties, containing 8 to ethenoxy radicals per mol ofdehydroabietinyl amine.

4. A semi-solid to paste-like solid, opaque composition as defined inclaim 7, suitable for use as a pickling inhibitor, containing 16 toethenoxy radicals per mol of dehydroabietinyl amine.

5. A warlike solid, opaque composition as defined in claim 7, suitablefor resolving water-in-oil emulsions, containing to mols of ethyleneoxide per mol of dehydroabietinyl amine.

6. A process for the preparation of a surface-active composition, whichcomprises condenstng dehydroab etinyl primary amine with 4 to 40 mols ofethylene oxide by heating at, a temperature from -180 C. m the presenceof an alkaline-reacting catalyst.

7. As a novel composition of matter soluble in water and having surfaceactive properties therein, a viscous liquid to wax-like solid,translucent to opaque N-polyethenoxylated dehydroabietinylaminecontaining 4 to 40 ethenoxy radicalsper molecule of said amine.

8. A viscous liquid to paste-like solid composition as defined inclaim7, having outstanding detergent properties, and containing 8 to 30ethenoxy radicals per molecule of dehydroabietinylamine.

9. A viscous liquid to semi-solid, translucent composition as defined inclaim 7, having outstanding detergent properties and containing 8 to 15ethenoxy radicals per molecule of dehydroabietinylamine.

References Cited in the file olE this patent UNITED STATES PATENTS2,194,429 Krzikalla Mar. 19, 1940 2,194,906 Krzikalla Mar. 26, 19402,510,063 Bried June 6, 1950 2,510,284 Haggard June 6, 1950 FOREIGNPATENTS 467,571 Great Britain June,,16, 1937 OTHER REFERENCES Borglin:Soap ang7Sanita1-y Chemistry, December 1947,

pp. 147, 149 and 1

1. AS A NOVEL COMPOSITION OF MATTER, SOLUBLE IN WATER AND HAVINGSURFACE-ACTIVE PROPERTIES THEREIN, AN N-POLYETHENOXYLATEDDEHYDROABIETINYL AMINE CONTAINING 4 TO 40 ETHENOXY RADICALS PER MOL OFSAID AMINE.